Condensation product and process of making same



Patented Feb. 12, 1935 UNITED STATES eATE T oFFicii CONDENSATION PRODUCT AND PROCESS 7 OF MAKING SAME Heinz Seheyer, Frankfort-on-the-Main, Germany, assignor to General Aniline Works, Inc.,' New York, N. Y., a corporation of Delaware No Drawing. Application October 18, 1932, Serial No. 638,391. In Germany December 2, 1930 4 Claims.

in which the anthraquinone nuclei may be substituted by monovalent substituents, such as halogen-, alkylor aryl-groups, and to a process of making these new condensation products.

The starting materials may be prepared according to the process described in U. S. Patent No. 1,646,782. The present new condensation products are obtained by treating said starting materials with an acid condensing agent, particularly either of the group consisting of an aluminum and ferric halide, suitable for the Friedel- Crafts reaction, at temperatures from about IOU-200 0., or of the group of sulfuric acid, such as chlorosulfonic acid or fuming sulfuric acid. The condensation reaction may be advantageously carried out with addition of a suitable diluent, such as sodium chloride in addition to the aluminum chloride and of a suitable oxidant such as manganese dioxide or halogen and the like.

Instead of starting from the aforesaid glyoxaldianthraquinone compounds (described in U. S. Patent 1,646,782) themselves, one may convert them previously into their claret-red to violet colored derivatives by treatment with an alkaline condensing agent according to U. S. Patent 1,709,- 956 and subsequently subject these alkaline condensation products to the action of an acid condensing agent. In this case sulfuric acid is a particularly suitable condensing agent.

In view of the properties of the new condensation products one may assume that an intramolecular condensation and formation of a new ring system has taken place during the reaction.

The new condensation products obtained ,according to my present process are quite diiferent from the initial products as regards their chemical behavior. In common therewith they are soluble in an alkaline hydrosulfite solution from Which the vegetable fiber is dyed intense brownish shades of a good fastness.

. The final products obtained by previously treatingthe initial products with an alkaline con- 5 densing agent and subsequently subjecting the products thus obtained to the action of an acid condensing agent generally have the same chemicalconstitution as those obtained by directly treating the starting materials with an acid condensing agent. Consequently the chemical and tinctorial behavior is generally the same. Only in some cases the'shade of dyeings obtained therewith is somewhat different owing probably to the fact that, when subjecting the initial products directly to an acid condensing reaction with the addition of an oxidant, a simultaneous entrance of halogen into the molecule of the new condensation products may occur, when working under such conditions that halogen is liberated from the reacting agents used.

In order to further illustrate my invention the following examples are given, the parts being by weight and all temperatures in centigrade degrees, but it is understood that my invention is not limited to the particular products'nor reacting conditions mentioned therein:

it in the vat and isolating it therefromin the usual manner. It dissolves in concentrated sulfuric acid with a violet color and dyes cotton from a yellowish brown vat reddish brown shades of a good fastness.

When carrying out the reaction at tempera-- tures beginning from about one needs a longer time of duration; one may likewise increase the temperature of reaction to about 200 and carry out the reaction with the addition of ferric chloride.

Example 2 10 parts of the condensation product, used as starting material in Example 1, are dissolved in about 400 parts of sulfuric acid monohydrate while cooling to about 12. 15 parts of potassium persulfate are added during 1 to 2 hours. The greenish blue color of the solution thereby turns .to reddish blue. The reaction product is isolated by pouring the reaction mass on ice and filtered 01f. It'represents a-reddish brown powder and dyes cotton from a brownish vat fast reddish,

By washing the raw product with V brown shades. warm chlorobenzene and alcohol it maybe purifled.

Example 3 11 parts of the condensation'product derived from 2-chloroanthrone andglyoxal are 'mixed with about 100 parts of aluminium chloride, 25 parts of sodiLun chloride and 4.2 parts of manganese dioxide of about 84% strength. The

mixture is slowly heated to about 140 and the mass is kept at this temperature for about half anhour. Thenewdyestuff, isolated as described in Example 1, dyes cotton from the vat reddish 7 brown shades which are very similar to those obtained with the dyestuff of Example 1.

A corresponding dyestuff is obtained, when usingas starting material the condensation product derived from 2-methylor 2-phenyl-anthrone and glyoxal.

Example 4 'Into amixture of about 100 parts-of aluminium chloride and 25 parts of sodium chloride while well stirring at about 140-? a strong current of chlorine and simultaneously'slowly 10 parts of the initial product'used in Example 3 are introduced.

Thereaction mass is kept for about half an hour at this temperature. dyes-cotton from a yellowish brown vat full reddish brown shades. V

A similar result isobtained, when simultaneously blowing air into-the reaction mass instead of introducing chlorine.

Example, 5

10 partsof. the initial product used in Examples 3 and 4 are introduced at about into about 300 parts of chlorosulfonic acid and the mixture is stirred for about an hour at this temperature, until the initial product has disappeared. Then the reaction mass is poured on ice and the formed precipitate is filtered off.- The reaction product represents a reddish brown powder, it dissolves in sulfuric acid with a reddish blue color and dyes. cotton from a brown vat fast reddish brown shades,

When'using as condensing agent a fuming sulfuric acid containing about 30% of free sulfur trioxide, in a similar manner a sulfonic acid derivativeof said dyestuff is obtained.

Example 6 U 10 parts of the initial product used in the foregoing Examples 3 to 5 are dissolved at room temperature in about 400 parts of a fuming sulfuric acid'containing only about 2% of free sulfur trioxide and at about 15 during about an hour 5 parts'of manganese dioxide are added, the bluish green color'of the solution thereby turning to reddish-blue, The reaction mass is poured on The dyestuff thus obtained ice and the formed precipitate is filtered off. The product thus obtained is identical with the product of Example 5. I

Example 7 11 parts of the condensation product derived from 2.6-dichloro-anthrone and glyoxalsulfate are mixed with about parts of aluminium chloride, 25 parts of sodium chloride and 8.4 parts of manganese dioxide. The mixture is heated at about The new dyestuif isolated as de-' scribed in the foregoing examples may be purified by converting it into the sulfate which. is

scarcely soluble in concentrated sulfuric acid,

separating the sulfate'from the more soluble impurities by filtration and decomposing it by addition of water. The new dyestuff dyes cotton from a yellowish brown vat brown shades.

Example 8 slowly heated to about 140 and kept at this tem-" perature until all starting material has .dis-

appeared. The condensation product is isolated in the customary'manner. It'forms when recrystallized from Intro-benzene. brown prisms,

' soluble in concentrated sulfuric acid-with a dichroic violet-red color. It dyes cotton from a yellowish brown vat reddish brown shades. The

dyestufl is very. similar with the dyestufi of Example 1. I

Example 9 7 When starting from the condensation product derived from .2-chloro-an throne and glyoxalsulfate and subjecting it to the action of an alcoholic caustic potash solution and subsequently-0f an aluminium-chloride fusion in the same manner as described in Example 5, the new dyestuff thus obtained forms when dry a brown powder recrystallizing from nitrobenzene in form of brown prisms. It dissolves in concentrated sulfuric acid with a bluish violet color and forms a yellowish brown vat from which cotton is dyed full reddish. brown shades. 'The dyestuif is verysimilar to those of Examples 3 to 6.. a

When introducing the alkaline reaction prod uct into concentrated sulfuric acid at about-140'-- 150", instead of treating it with aluminium chloride, the final product is very smoothly formed.

Example 10 V The condensation product derived from an throne and glyoxal is treated with an alcoholic caustic potash solution assaidin Example '8. 10 parts of this condensationproduct are introduced at about into about 100 parts. of'concentrated sulfuric acid. The greenish coloration of the solution thereby almost immediatelyturris V to violet. The reactionmass is kept for a short" time at this temperature and thencool'ed'down and poured on ice. The dyestufi separatesin the form of brown flakes, it is filtered off, washed out and dried. It corresponds in its properties with the product of. Example 8. But according to the conditions applieda simultaneous sulfo= nation takes place toa greater or lesser extent.

in which the anthraquinone nuclei may be substituted by halogen atoms or an alkylor arylgroup, which condensation products are when dry brownish powders, which are recrystallizable from organic solvents of a higher boiling point, soluble in concentrated sulfuric acid with a violet to bluish color and in an alkaline hydrosulfite solution with a yellowish brown color from which the vegetable fiber is dyed brown shades of a good fastness and which condensation products are obtained by subjecting said initial materials to an alkaline condensation reaction and the products thus obtained to an acid condensation reaction.

2. Condensation products derived from glyoxal-dianthraquinone compounds of the formula:

in which the anthraquinone nuclei may be substituted by halogen atoms or an alkylor arylgroup, which condensation products are when dry brownish powders which are recrystallizable from organic solvents of a higher boiling point, solublev 3. Condensation products derived from glyoxal-dianthraquinone compounds of the formula:

0 CH-O H- O in which the anthraquinone nuclei may be substituted by halogen atoms or an alkylor arylgroup, which condensation products are when dry brownish powders which are recrystallizable from organic solvents of a higher boiling point, soluble in concentrated sulfuric acid with a violet to bluish color and in an alkaline hydrosulfite solution with a yellowish brown color, from which the vegetable fiber is dyed brown shades of a good fastness and which condensation products are obtained by subjecting said initial materials without isolation of an intermediate formed by alkaline condensation to the action of an acid condensing agent with the addition of an oxidant.

4. The condensation product derived from the glyoxal-dianthraquinone compound of the formula:

O CH-CH O which condensation product is when dry a brownish powder which is recrystallizable from organic solvents of a higher boiling point, soluble in concentrated sulfuric acid with a dichroic red-violet color and in an alkaline hydrosulfite solution with a yellowish brown color from which the vegetable fiber is dyed brown shades of a good fastness and which condensation product is obtained by subjecting said initial material to an alkaline condensation reaction and the product thus obtained to an acid condensation reaction.

HEINZ SCHEYER. 

